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  • 1
    ISSN: 1434-1948
    Keywords: Organometallic compounds ; Nickel complexes ; Crystal structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The compound cis-[Ni(C6F5)2(PhCN)2] has been used as the starting material for the preparation of the bimetallic complexes [(C6F5)2Ni(μ-X)2Ni(C6F5)2]2- (X = SCN, OCN, N3), [(C6F5)2Ni(μ-SCN)2Pd(C6F5)2]2-, [(C6F5)2Ni(μ-NCS)2Pd-(dppe)] [dppe = 1,2-bis(diphenylphosphanyl)ethane], and the trimetallic[(C6F5)2Ni(μ-NCS)2Pd(μ-SCN)2Ni(C6F5)2]2-. The mononuclear compounds [(C6F5)2NiLX] (L = PPh3, P(C6H4MeO-p)3; X = SCN, OCN) are obtained by reaction between [(C6F5)2Ni(&μ-X)2Ni-(C6F5)2]2- and L. The treatment of cis-[Ni(C6F5)2(PhCN)2] with [M(SAr)2(dppe)] leads to the formation of the arylthiolate complexes [(C6F5)2Ni(μ-SAr)2M(dppe)] (Ar = Ph, C6H4Me-p, C6H4NO2-p; M = Ni, Pd, Pt). The X-ray diffraction study of [(C6F5)2Ni(μ-SPh)2Pd(dppe)] shows that both metal atoms, Ni and Pd, are coordinated in a slightly distorted square-planar geometry and the μ-thiolato groups are in the syn conformation.
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  • 2
    ISSN: 1434-1948
    Keywords: Cyclopropanation ; Copper ; N ligands ; Macrocycles ; Supported catalysts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CuI and CuII complexes of cyclic and open-chain polyaza compounds have been tested as catalysts in the benchmark cyclopropanation reaction of styrene with ethyl diazoacetate. In general, only small amounts of copper are needed to promote the reaction. The catalytic activity depends on the structure of the ligand, e.g. amine-amides are more efficient than polyamines, and on the oxidation state of copper, CuII being more active than CuI. Given that CuI is the active species, these changes of behavior must be related to the stabilities of the complexes. The nature of the counterion also has a noticeable influence on the catalytic activity, the role of which is discussed. XAS measurements suggest the formation of oligomeric species. Some of the chiral ligands lead to small enantiomeric excesses. Open-chain ligands can easily be supported on organic polymers and their complexes can be used as catalysts. Furthermore, cyclic and acyclic complexes can be supported on clays by cation exchange and the solids obtained tend to promote the reaction with a decrease in the trans/cis ratio.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 368-376 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A proposed theoretical model describes colloids deposition on a membrane surface accounting for surface interactions. A mass-transfer equation links the deposition rate to hydrodynamic conditions (permeation and tangential flow through a boundary layer thickness, δ) and to physicochemical properties of the suspension (diffusion, D, and potential barrier between particles, VB). This equation predicts the existence of a critical flux, Jcrit, for ultrafiltration, reverse osmosis, or microfiltration of large-size colloids as: \documentclass{article}\pagestyle{empty}\begin{document}$$ J_{crit} = \frac{D}{\delta}ln \left({\frac{{V_B}}{\delta}} \right) $$\end{document} Some of the trends observed when processing protein solutions are explained by this model. Previous experimental data for various colloids or our data with a clay suspension in the presence of electrolytes are also compared to predictions of our model. It explains the “flux anomaly” for particle sizes between 10 nm and 1 μm.
    Additional Material: 10 Ill.
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  • 4
    ISSN: 0947-3440
    Keywords: Indazolols ; Indazolinones ; Indoxyls ; Cytostatic agents ; HeLa cells ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The remarkable cytostatic activity of 1-substituted indazolols 2a,b, condensed indazolinones 4a-c and indoxyl derivatives 5a, b against HeLa cells is reported. Three different approaches to the synthesis of indazolophthalazinone 4a, representing alternatives to those previously reported, were studied. Several compounds related to the mentioned indazolols and indazolinones were obtained and their cytostatic activity against HeLa cells was tested. Among them we can mention the tetracyclic SO2 analogue 14 and the condensed pyridine derivative 18, the tricyclic pyrazolophthalazinone 22 and the bicyclic pyrazolodiazepinone 25, which were prepared by taking advantage of the reactivity of heterocyclic spiro aminimides.
    Additional Material: 1 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Advanced Materials 7 (1995), S. 111-119 
    ISSN: 0935-9648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 60 (1998), S. 156-168 
    ISSN: 0006-3592
    Keywords: fed-batch ; Candida rugosa lipase production ; control ; feeding strategy ; on-line monitoring and estimation ; lipase purification ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Simulation studies have predicted that maximum lipase activity is reached with fed-batch operation strategies. In this work, two different fed-batch operational strategies have been studied: constant substrate feeding rate and specific growth rate control. A constant substrate feeding rate strategy showed that maximum aqueous lipolytic activity (55 U/mL) was reached at low substrate feeding rates, whereas lipase tends to accumulate inside the cell at higher rates of substrate addition. In the second fed-batch strategy studied, a feedback control strategy has been developed based on the estimation of state variables (X and μ) from the measurement of indirect variables such as CER by means of mass spectrometry techniques. An on-off controller was then used to maintain the specific growth rate at the desired value by adjusting the substrate feeding rate. A constant specific growth rate strategy gave higher final levels of aqueous lipolytic activity (117 U/mL) at low specific growth rates. At higher specific growth rates the enzyme remained accumulated inside the cell, as was observed with a constant feeding fed-batch strategy. With a constant specific growth rate strategy, lipase production by Candida rugosa was enhanced 10-fold compared to a batch operation. Purification studies have demonstrated that lipolytic and esterasic specific activity ratios of Candida rugosa isoenzymes can be modified by using different operational conditions. These studies have also showed that the isoenzymes obtained in a controlled growth rate strategy are around three- to four-fold more active than those obtained in a constant feeding rate strategy. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 60: 156-168, 1998.
    Additional Material: 7 Ill.
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  • 7
    ISSN: 0006-3592
    Keywords: nitrate removal ; Klebsiella oxytoca ; Arthrobacter globiformis ; dinitroethylene glycol ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two strains, a gram-negative bacterium Klebsiella oxytoca CECT 4460 and a gram-positive, mycelium-forming bacterium Arthrobacter globiformis CECT 4500, tolerant to up to 1 M nitrate, were isolated from the grounds of a munitions factory. Under strict aerobic conditions and with appropriate C-sources, growth of these bacteria took place when the nitrate concentration in the medium was below 150 mM. Optimal growth conditions regarding the culture medium composition for the biological removal of nitrate were established in batch cultures. Then, the system was scaled up to a 40-L pilot plant and operated under continuous conditions in a factory with direct waste streams from dinitroethylene glycol production after appropriate dilution with nontreated groundwaters. The level of nitrate in the effluent was below 0.5% of the initial N-load. Nitrite and ammonium were undetectable and the level of the C-source in the effluent was below 50 mg per L. On the basis of these results, we conclude that the system worked on site satisfactorily. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 58: 510-514, 1998.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 55 (1997), S. 252-260 
    ISSN: 0006-3592
    Keywords: lipase ; chemical modification ; stability ; esterification ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Semipurified lipase of Candida rugosa (CRSL) was subjected to chemical modification, and the activities of the modified lipase, in hydrolysis and esterification reactions, were examined. The esterification reactions were carried out in the absence and presence of isooctane. When the enzyme was modified with polyethylene glycol (PEG), two methodologies were studied. The activation of PEG with p-NO2-phenylchloroformate gives better biocatalysts than those obtained with cyanuric chloride-PEG. The chemical modification with PEG increases the stability of pure lipases in isooctane at 50°C (extreme conditions). The chemically modified enzymes are useful for biotransformations in organic solvents. In addition the nitration of tyrosines with tetranitromethane was also studied. © 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 252-260, 1997.
    Additional Material: 5 Ill.
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  • 9
    ISSN: 0006-3592
    Keywords: tubular photobioreactors ; light distribution ; average solar irradiance ; light attenuation ; microalgae mass culture ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model to estimate the solar irradiance profile and average light intensity inside a tubular photobioreactor under outdoor conditions is proposed, requiring only geographic, geometric, and solar position parameters. First, the length of the path into the culture traveled by any direct or disperse ray of light was calculated as the function of three variables: day of year, solar hour, and geographic latitude. Then, the phenomenon of light attenuation by biomass was studied considering Lambert-Beer's law (only considering absorption) and the monodimensional model of Cornet et al. (1900) (considering absorption and scattering phenomena). Due to the existence of differential wavelength absorption, none of the literature models are useful for explaining light attenuation by the biomass. Therefore, an empirical hyperbolic expression is proposed. The equations to calculate light path length were substituted in the proposed hyperbolic expression, reproducing light intensity data obtained in the center of the loop tubes. The proposed model was also likely to estimate the irradiance accurately at any point inside the culture. Calculation of the local intensity was thus extended to the full culture volume in order to obtain the average irradiance, showing how the higher biomass productivities in a Phaeodactylum tricornutum UTEX 640 outdoor chemostat culture could be maintained by delaying light limitation. © 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 701-714, 1997.
    Additional Material: 15 Ill.
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  • 10
    ISSN: 0006-3592
    Keywords: solar irradiance ; tubular photobioreactor ; microalgal culture ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A macromodel is developed for estimating the year-long biomass productivity of outdoor cultures of microalga in tubular photobioreactors. The model evaluates the solar irradiance on the culture surface as a function of day of the year and the geographic location. In a second step, the geometry of the system is taken into account in estimating the average irradiance to which the cells are exposed. Finally, the growth rate is estimated as a function of irradiance, taking into account photoinhibition and photolimitation. The model interconnects solar irradiance (an environmental variable), tube diameter (a design variable), and dilution rate (an operating variable). Continuous cultures in two different tubular photobioreactors were analyzed using the macromodel. The biomass productivity ranged from 0.50 to 2.04 g L-1 d-1, and from 1.08 to 2.76 g L-1 d-1, for the larger and the smaller tube diameter photobioreactors, respectively. The quantum yield ranged from 1.1 to 2.2 g E-1; the higher the incident solar radiation, the lower the quantum yield. Simultaneous photolimitation and photoinhibition of outdoor cultures was observed. The model reproduced the experimental results with less than 20% error. If photoinhibition was neglected, and a growth model that considered only photolimitation was used to fit the data, the error increased to 45%, thus reflecting the inadequacy of previous outdoor growth models that disregard photoinhibition. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 58: 605-616, 1998.
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